Electrowinning circuit and method for gathering of metal of interest  by an ionic exchange interface

ABSTRACT

A metallurgical method for operating an autogenous production circuit for producing metal(s), said method using one or more oxidizing agents generated electrolytically in a cell with one or more interfaces which allows anion exchange; said method comprising steps of: (a) leaching of mineral(s) or material(s) containing at least one metal of interest (LX) in a first cell (A) to produce a pregnant leach solution ( 2 ) and an acid-ferrous aqueous solution ( 8 ); (b) using solvent extraction process(es) or selection process(es) in a second cell (B) to concentrate said metal(s) of interest (SX) of said pregnant leach solution ( 2 ) to produce a rich electrolyte ( 5 ) and a raffinate solution ( 4 ), said raffinate solution ( 4 ) being recycled in said first cell (A); and (c) electrowinning (EW) in a third cell (C) of said rich electrolyte ( 5 ) received from said second cell (B) and said acid-ferrous aqueous solution ( 8 ) received from said first cell (A), for producing a metal cathode ( 6 ) and an acid-ferric acid solution ( 9 ), said acid-ferric acid solution ( 9 ) being recycled in said first cell (A), wherein said steps (a), (b) and (c) are performed in said autogenous circuit that includes said first, second and third cells (A, B, C) with one or more anionic interfaces producing anodic and cathode reactions.

Hydrometallurgical processes for the treatment of ores, concentrates andmaterials involve various relevant operations, such as: leaching ordissolution of the metal of interest, performed in piles and reactors,the concentration and purification of the solutions by solventextraction and ion exchange; and finally, the synthesis of metal ormetal compound desired by the use of precipitation, crystallization orelectrowinning.

Industrial processes commonly use a suitable environment for dissolutionand support themselves in conditions that are favorable for the leachingprocess, concerning: gases, temperature, microorganisms, mechanicalprocesses, etc. These processes are used in the copper case and othermetals, with the oxidant agent being ferric sulfate.

Generally, metals of interest in the solution are in presence of otherspecies. Some of these species contain ions that support thehydrometallurgical process in order to achieve electrowinning. However,in most cases, these species contain ions that inhibit or do not allowthe electrowinning to occur in a proper way.

Leaching processes in the mining industry occur at higher rates thanthey do in nature, but high investments and operational costs (energy,abrasives, corrosive solutions, etc.) are needed in order to maintainthe operations.

The patents that support these statements are the following: CESL, UBC,HPAL-Angloamerican, Dynatec, etc. (U.S. Pat. No. 5,730,776; No.6,503,293; No. 6,755,891; No. 7,125,436).

Other known hydrometallurgical processes include bio-leaching that usemicroorganisms, which are autogenous in the use of reagents such assulfuric acid and ferric sulfate for sulfur ores. However, theseprocesses require large scale equipments and installations and highstocks of materials and solutions in the industrial circuits in order toavoid the high residency times of the slow leaching velocity that isproduced in weak solutions with help of the oxidizing bacteria from theiron and sulfur compounds present in the minerals.

The references that support these statements are the following: U.S.Pat. No. 7,160,354; Batty & Rorke “Development and CommercialDemonstration of the BioCOP™ Thermophile Process”).

The processes of mineral dissolution that use ferric ion as a oxidizingagent are Galvanox, Albion and Brenda, which use pyrite, oxygen and/orchloride gas to periodically regenerate the oxidizing agent. The maindisadvantages of these processes are the high consumption of compressedair, the high consumption of sulfuric acid and the high expenses thatrepresent the use of chloride gas. The Brenda process commonly used toclean molybdenum concentrates, also requires closed installations andequipment and also materials resistant to this highly corrosivechlorinated environment (Cl₂-FeCl₃-H₂SO₄).

The patents and publications that support these statements are thefollowing: U.S. Pat. Nos. 3,674,424; 4,115,221; 5,993,635; 6,833,021;Chilean patent No. 33,924; Habashi (1993); Gupta (1992); IMOA (2008);Sutulov (1980) and Lundström et al., (2005); Dixon and Tshilombo (2005);Dixon et al., (2007).

In the copper case, as an illustration and without loss of generality,in FIG. 1, the main hydrometallurgical operations used in conventionalprocesses for the processing of sulfur copper minerals are illustratedin general terms.

The legends of FIG. 1 correspond to:

a. Main Operations: A-Leaching or Bioleaching in Piles and/or Dumps,B-Solvent Extraction and C-Electrowinning.

b. Main Currents or Flows: 1-Sulfur Mineral, 2-PLS Solution, 3-DiscardedMaterial, 4-Raffinate Solution, 5-Rich Electrolyte, 6-Copper Cathodesand 7-Weak Electrolyte.

Flow 1 of FIG. 1, contains Sulfur Minerals which are fed to Sub ProcessA in FIG. 1. Sub Process A consists in Leaching or Bioleaching in Pilesand/or Dumps.

From the Leaching produced in Sub Process A, as an example and withoutloss of generality, a solution containing copper sulfate (CuSO₄) isobtained at a concentration of 1-10 g/L, which in the industry is knownas PLS (Pregnant Leach Solution) and is represented by Flow 2 in FIG. 1.

Flow 3 corresponds to Discarded Material of the Leaching process; thismaterial is transported to Dumps where a second process of Leachingcould be attempted.

Flow 2 in FIG. 1 is fed to the Solvent Extraction plant that isindicated as Sub Process B in FIG. 1. At this stage the solution thatcomes from the Leaching Piles is liberated from its impurities and itscopper content is concentrated, passing from 1-10 g/L to 40-50 g/L, byusing extracting agents. In order to extract the copper from the PLSsolution, this is mixed with an organic solution (mixture of extractantand high flashpoint paraffin; 10-20% vol). The extracting agent capturesthe copper ions (Cu²⁺) in a selectively and generates a weak coppersolution (Cu <0.5 g/L) which is known as Raffinate Solution (Flow 4),which is conditioned and recycled to the Leaching process. Later, usingan acid Weak Electrolyte solution (Flow 7) the copper is released fromthe extractant, generating Flow 5 which is the Rich Electrolyte.

The Rich Electrolyte (Flow 5) with 40-50 g/L Cu is processed byconventional Electrowinning (Sub Process C) to obtain the main productwhich is Copper Cathodes of high purity (99,99% Cu) (Flow 6). A solutiondefined as Weak Electrolyte (Flow 7) is generated as a sub product; itwill be recycled to the Solvent Extraction Sub Process B for its copperre-concentration.

As a summary, it its mentioned that the Leaching process of mineralsand/or concentrates have the inconvenience that the regeneration of theoxidizing agent is complex in terms of investment and the additionaloperating equipment needed; also expensive because it is necessary toregenerate or constantly supply the oxidizing agent and even addingsulfuric acid in some cases.

On the other hand, the conventional Electrowinning process presents somedisadvantages: Low mass transfer rate because of the low agitationapplied in industrial cells, low specific surface of the flat cathodes 1m×1 m that are used and high consumption of electric energy (1.8-2.6kWh/Cu kg), promoted by the formation of acid mist when the water isdecomposed over the anode.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a metallurgicalmethod for operating an autogenous production circuit for producingmetal(s), said method using one or more oxidizing agents generatedelectrolytically in a cell with one or more interfaces which allowsanion exchange, said method comprising steps of:

(a) leaching of mineral(s) or material(s) containing at least one metalof interest (LX) in a first cell to produce a pregnant leach solutionand an acid-ferrous aqueous solution;

(b) using solvent extraction process(es) or selection process(es) in asecond cell to concentrate said metal(s) of interest of said pregnantleach solution to produce a rich electrolyte and a raffinate solution,said raffinate solution being recycled in said first cell; and

(c) electrowinning in a third cell of said rich electrolyte receivedfrom said second cell and said acid-ferrous aqueous solution receivedfrom said first cell, for producing metal cathodes and an acid-ferricacid solution, said acid-ferric acid solution (9) being recycled in saidfirst cell,

-   -   wherein said steps (a), (b) and (c) are performed in said        autogenous circuit that includes said first, second and third        cells with one or more anionic interfaces producing anodic and        cathode reactions.

The solution circuit is closed between the different indicated steps.Mineral(s) or material(s) enter to be treated in the leaching stage (LX)and in general also a solution from the (SX) circuit and a one from the(EW) circuit with the oxidizing agent(s). This with the purpose ofLeaching Metal(s) and material(s) and/or improve the grade of thecompound(s) to be treated. To the Electrowinning stage, with thepresence or not of separate chambers for the ionic exchange, enters aconcentrate solution of the Metal(s) of interest; this solutioncorresponds to the Rich Electrolyte or catholyte and an aqueous solutionof the lowest ion valence of the oxidizing agent(s). The use of anelectric current allows the reduction of the Metal dissolved in thecathode and the simultaneous oxidation of the agent(s) that turn intodissolved oxidizing agent(s) over the surface of the anode and thisoxidizing agent is recycled into the circuit so it can be reused in theLeaching process or other if suitable for the production needed. Thecircuits, with the purpose of maintaining a stable and high performanceenvironment, may or may not incorporate unit operations (withoutlimitations) of exchange (in and/or out) of mass and/or energy over thecircuit described. Also, mechanisms and algorithms of control may or maynot be used to achieve the effect wanted in an optimized way.

According to another aspect of the present invention, there is provideda method for use in an autogenous productive circuit configuration forthe production of sulfur metals and materials that use ferric sulfate asan oxidizing agent generated electrolytically in a cell with ionicexchange membrane, said method comprising steps of: (a) acid-ferricleaching of the mineral or material including at least one of compounds,concentrates, tailings, white metal, cements, precipitates, scrap andsulfur minerals, through a conventional system ofpiles/dumps/reactors/vats; (b) solvent extraction (SX) to separate arich electrolyte coming from the metal of interest (Cu, Mn, Zn, Co, Mo,Ni, etc.), (c) electrowinning (EW) done in a circuit of cells withanionic membranes for the production of Metal Cathodes. A raffinatesolution enters the leaching stage coming from the SX circuit or otherdevice and also a ferric solution coming from EW, where Metals areleached and/or the grade of the material or compound treated isimproved. To the electrowinning stage a purified and concentrated (inthe Metal Cu, Co, Mn, Mo and/or Zn among other metals and compounds)acid solution enters (this solution corresponds to the Rich Electrolyteor catholyte) and also an aqueous solution of sulfuric acid anddissolved ferrous sulfate or, anolyte. The use or an electric currentallows the reduction of the Metal dissolved in the cathode and thesimultaneous oxidation of the iron dissolved over the surface of theanode.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram illustrating the main hydrometallurgicaloperations used in conventional processes for the processing of sulfurcopper minerals.

FIG. 2 is a block diagram illustrating an autogenous process accordingto a preferred embodiment of the present invention.

FIG. 3 is a block diagram illustrating an autogenous process accordingto another preferred embodiment of the present invention

THE INNOVATIVE PROCESS PROPOSED

The autogenous process disclosed in the present application involvesleaching or dissolving compounds, concentrates, materials and minerals(considering metals)—such as: Cu, Mn, Zn, Co, Mo, Ni which are going tobe referred to generally as Metals—by using oxidizing agents; which ispossible to regenerate directly during the production of metalliccathodes and be used again as oxidizing agent in the leaching stage, bythe use of one or many interfaces that are constituted by anionicmembranes in an electrolytic cell. The circuits may or may not containunit operations for the exchange of mass and energy. In FIG. 3, thisgeneral and base scheme is presented, which as an illustration andwithout loss of generality, shows an autogenous process according to apreferred embodiment of the present invention.

A process according to another preferred embodiment of the presentinvention, as a general and base scheme, is also presented graphicallyin FIG. 2.

FIG. 3 presents a General Scheme of the Autogenous Process Proposed forLeaching Compounds, Concentrates and/or Metals. Without loss ofgenerality and as an example, the legends in FIG. 3 correspond to sulfurcopper Minerals that allow the production of Copper Cathodes:

-   -   i) Main Operations: A-Leaching or Bioleaching in Piles and/or        Dumps, B-Solvent Extraction and C-Electrowinning.    -   ii) Main Currents or Flows: 1-Material, Mineral, Concentrate or        Dust with copper or other Metals, 2-PLS Solution, 3-Discarded        Material, 4-Raffinate Solution, 5-Rich Electrolyte, 6-Copper        Cathodes and 7-Weak Electrolyte, 8-Acid-Ferrous Aqueous Solution        and 9-Acid-Ferric Aqueous Solution.

Two different solution circuits are available in Sub Process C and theyare separated by a selective membrane. The purpose of this circuitdesign this is to balance the different operations in terms of theamount of acid and iron being dissolved, in addition to generating aRich Electrolyte of the metal of interest (in some cases, there is morethan one metal of interest) by means of the Solvent Extraction (SX)process, which separates the dissolved iron and other impuritiescontained in the PLS Solution that comes from Leaching. Indeed, FIG. 3contains two independent inner circuits:

Circuit A: Consists on Flow 8 and Flow 9

Circuit B: Consists on Flow 2, Flow 5, Flow 7 and Flow 4.

The Acid-Ferrous Aqueous Solution (Flow 8) is transformed into theAcid-Ferric Aqueous Solution (Flow 9) in Circuit A because of theinteraction with Circuit B in Sub Process C; this is where the selectiveionic exchange of sulfate ion (SO₂ ⁻⁴) occurs because of the interface(membrane), that allows the ionic exchange without mixing the twodifferent circuits.

In the electrolytic cell membrane semi-reactions are:

-   -   i) anodic reaction: 2Fe2+--->++2e2Fe3    -   ii) cathode reaction: Cu2++2e--->Cu°

In FIG. 3, as an example and without loss of generality, two unitoperations are illustrated:

Unit Operation M: Located in Flow 9, extract/incorporate mass from/intothe flow.

Unit Operation E: Located in Flow 8, extract/incorporate energyfrom/into the flow.

However, in FIG. 3 it is possible to incorporate new Unit Operations, tovary the circuits and/or flows and add control algorithms in order to:(a) achieve balance of mass and energy and (b) optimize operations.Without loss of generality, some examples would be: If a solution has anexcess of iron, lack of sulfur or if a higher temperature is needed tooptimize the Leaching process.

Flow 1 in FIG. 3, contains Material, Mineral, Concentrate or Dust withcopper or other Metal which are fed to the Sub Process A. Sub Process Aconsists on an acid-ferric leaching circuit in Reactors, Piles or Dumps.Here the materials containing Metals are leached by applying acidsolutions (Flow 4) and ferric solutions (Flow 9) from the SolventExtraction circuit (Sub Process B) and Electrowinning (Sub Process C).

From de Leaching produced in Sub Process A, as an example and withoutloss of generality, a solution containing copper sulfate (CuSO₄) isobtained at a concentration of 1-10 g/L which in the industry is knownas PLS and is represented by Flow 2 in FIG. 1.

Flow 3 corresponds to Discarded Material of the Leaching process; thismaterial is transported to Dumps where a second process of Leachingcould be attempted.

Flow 2 is fed to a Solvent Extraction circuit, which is indicated as SubProcess B in FIG. 2. At this stage the solution that comes from theleaching is cleaned of impurities and concentrates its copper content,reaching 40-50 g/L Cu, by using extracting agents. To remove the copperfrom the PLS solution, it is mixed with a solution of organic (a mixtureof extractant and high flash point paraffin, 10-30% vol.). Theextracting agent captures the copper ions (Cu⁺²) selectively andgenerates a weak copper solution (Cu <0.5 g/L), known as RaffinateSolution (Flow 4), which is conditioned and recycled to the Leachingprocess. Subsequently, using a Weak Electrolyte acid solution (Flow 7)copper is discharged from the extractant, generating Flow 5 which is theRich Electrolyte.

The Rich Electrolyte (Flow 5) with 40-50 g/L Cu concentration and theAcid-Ferrous Aqueous Solution (Flow 8) are processed by Electrowinningin a circuit with electrolytic cells with membrane (Sub Process C) inorder to obtain the primary product consisting of a pulp or CopperCathodes of high purity (99.99% Cu) (Flow 6). As sub-products of this:(a) A solution called Weak Electrolyte (Flow 7) is generated in thecathodic compartment, this solution is recycled to Solvent ExtractionSub Process B for its re-concentration of copper. (b) An Acid-FerricAqueous Solution (Flow 9) in the anode compartment is generated, whichis recycled to the leaching circuit (Sub Process A). For more details ofMembrane Electrowinning process see the developments by Cifuentes et al.2004 and 2007 and Casas et al., 2008. Developments in the field of ionexchange membranes used in Electrowinning processes in cells withmembrane (electrodialysis processes) can be found in the references ofLorrain et al, 1996 and Krol 1997.

In the electrolytic cell membrane semi-reactions are:

-   -   i) anodic reaction: 2Fe2+--->++2e2Fe3    -   ii) cathode reaction: Cu2++2e--->Cu°

Each semi-reaction occurs separately in its anion and cationcompartment, respectively, which are separated by adding an anionicmembrane located between the two compartments. This membrane isselective and allows the exchange of sulfate anions (SO₄ ⁻²) from thecatholyte to the anolyte, so as to achieve electro neutrality in thesolutions while the electrolytic process of copper cathode formationdevelops and allowing recovery of the oxidizing agent ferric sulfate inFlow 9.

The capacity of the circuit as a whole allows the processing of sulfurminerals and concentrates of lower copper grades, which the industry iscurrently not being able to treat by means of hydrometallurgicalprocesses. The new process achieves at a low cost a circuit thatminimizes the Discard Material flow because it balances the differentflow involved and uses Electrowinning cells with an interface, inparticular using a membrane that allows regeneration of the oxidizingagent and therefore produce copper cathodes with less electric energyconsumption.

This new process (see FIG. 3), that incorporates in this patentapplication new unit operations to achieve optimized mass and energybalance, is based on the process illustrated in FIG. 2 and allows tosolve different problems of the extractive metallurgic industry in termsof the processing of minerals, sub-products and Metals that require theuse of an oxidizing agent. In this patent application, as an example,the autogenous process uses the highly oxidizing ferric sulfate, whichis recycled into the circuit at a low cost making possible theprocessing of additional resources compared to conventionalhydrometallurgical technologies, incorporating or extracting mass and/orenergy.

The procedure outlined, in addition to the usual materials, is suitablefor processing various others materials and metallurgic resources likefor example: scrap metal, cement, metal, foundry slag, shafts, matte andwhite metal casting, casting powders, anode sludge and sulfide minerals,in a circuit that includes acid-ferric leaching of these materials,generating rich solutions that are purified and concentrated withconventional technology of solvent extraction.

The Acid-Ferrous and Rich Electrolyte solutions obtained are processedby Electrowinning cells modified with the addition of ion exchangemembranes to produce cathodes of metals and the regeneration of theoxidizing solution (Acid-Ferric solution) used in the Leaching materialslisted.

Descriptions of the operation and performance of these electrolyticmembrane cells are found in the following publications and patents:

U.S. Pat. No. 5,961,833; No. 6,306,282;No. 6,355,175; No. 3,957,504; No.4,684,450; No. 4,968,008; No. 5,039,337; No. 5,372,684; No. 5,718,874;No. 5,762,683; No. 5,492,608; No. 6,159,356; No. 7,368,049. Europeanpatents: EPO 415482 A1; ES 2 035. Chilean patent No. 336; Chilean patentapplication 199600852. Papers: Cifuentes et al., (2004, 2007), Lorrainet al., (1996) and Krol et al., (1997).

It is noteworthy that in the consulted papers and patents there is nodisclosure or use of a circuit incorporating unit operationconfigurations as the ones proposed in this patent application. Thereare several processes that use ferric sulfate as an oxidizing agent;however, this reagent is generated inside the Leaching reactor throughthe application of oxygen and temperature, chlorine or by usingiron-oxidizing microorganisms. Also, the developments made in theelectrolyte membrane reactors to produce Metal Cathodes, focus on celldesign and its various operating conditions, not considering the aspectsof overall balance in a circuit of self-processes in terms of balanceduse of the oxidizing agent from Leaching to Electrowinning operations,which corresponds to the innovation presented in this patentapplication.

The current state mentioned in the consulted bibliography and patentdocuments (U.S. Pat. No. 7,368,049, U.S. Pat. No. 6,159,356 and U.S.Pat. No. 5,494,608) describe processes which do not produce ferricsulfate in high concentrations. On the other hand, in the proposedpatent application this is a new possibility, which allows using theferric sulfate (produced in the new Electrowinning) in the Leachingprocess where it is going to be reduced into ferrous sulfate.

Thus, specifically an interface, in particular and without loss ofgenerality based membrane, allows the interchange(s) ionic(s)specified(s) that simultaneously generate or re-oxidizing agent(s) withreactions in the camera (or without camera) of catholyte in the camera(or without camera) anolyte, goal the metal electrowinning of interestat a low operational cost.

The differences between the patent (U.S. Pat. No. 7,368,049) and the onepresented are:

(U.S. Pat. No. 7,368,049) Present Application There is a single flowthat passes Two flows separated by a through the anode. There is nomembrane interface at the interface present at the electrowinningElectrowinning stage. stage. Ferric sulfate generated is mixed with Theferric sulfate flow generated the Weak Electrolyte that also has a highconcentration and is contains copper; it cannot be reused recycled intoLeaching. later for Leaching. Requires an additional process to Does notrequire such a process. remove the acid generated in electrowinning.

It is noteworthy that the present application also applies to variousmetals such as: Zn, Co, Ni, Mn, Mo, among others. The proceduresindicated in the patents U.S. Pat. No. 7,368,049 and U.S. Pat. No.6,159,356 are also applicable to the copper case.

This process is highly versatile concerning to the type of metallurgicalresource to be processed and is built in a modular way for eachapplication of industrial interest, through a system that uses acombination of stages, series-parallel schemes of its componentequipments and recycling of the solutions to the different parts of thecircuit, to achieve a circuit configuration that allows precise balanceof the materials in the process (closed circuit, without discardingcontaminants).

The proposed process (among other things, depending on the oxidizingagent and specific ions in the ionic exchange) can be used for theproduction of metallic cathodes and/or base metal powders, such as: Cu,Zn, Co, Ni, Mo; materials and metallurgical products (concentrates ofCu, Zn, Co, Ni, Mo; intermediate materials of the smelters, slag, whitemetal, anode sludge). This production can be done adjusting its coppergrade and level of impurities to commercial values.

The present patent application has as an innovation the use of a cellwith one or many interfaces, generally composed of an ionic membranethat regenerates in a clean way the ferric sulfate solution (anolyte),which when is free of copper it can be reused directly for the Leachingof minerals, concentrates and materials that contain copper or otherMetals.

The main supplies required for the proposed process are: Leachingmetallurgical materials, electricity, process water, technical gradesulfuric acid, ferrous sulfate (initial filling of the pond and smalloffset potential losses), anion exchange membrane (initial and annuallyreplenished) and Solvent extraction SX (initial filling of the pond andsmall potential losses and evaporation), Electrowinning additives (tunerguar bean type), replacement of anodes (graphite or equivalent) andcathode foils mother/white (stainless steel sheets).

The technical problem and the invention in this patent applicationconsist in:

-   -   i) An autogenous process to leach or dissolve compounds,        concentrates, materials and minerals through the use of        oxidizing agents.    -   ii) The oxidizing agents regenerate directly during the        production of metallic cathodes in a chamber using one or many        interfaces that allow the processing of a solution with one or        many oxidizing agents suitable for the mineral of interest.

The invention is centered in the circuits, being the recycling of theoxidizing agent, without loss of generality, ferric sulfate, necessaryto support the process of metal dissolution, so an integral andsustainable process was designed and it allows the regeneration of theoxidizing agent taking advantage of a part of the energy necessary toachieve the production of the cathode. For achieving this production anelectrolytic cell with interface(s) is needed; without loss ofgenerality, membranes that allow ionic exchange. It is noteworthy thatthe configurations of the autogenous hydrometallurgical processesproposed in this patent application the ones that constitute and must beconsider in the inventive analysis. These configurations are not knownin the metallurgical industry and do not include the existence of unitoperations, in the flows that constitute the circuits, that contributeto the mass and energy balances required to optimize the process ofgathering cathodes of the metal of interest.

The configuration of new autogenous processes formulated in this patentapplication allows to solve different problems of the extractivemetallurgical industry in terms of the processing of mineral resources,sub-products and metals that require the use of an oxidizing agent. Inthis application of an autogenous process as an example, without loss ofgenerality, the highly oxidizing agent ferric sulfate is used andrecycled into the circuit at a low cost, allowing the processing ofadditional resources unlike conventional hydrometallurgicaltechnologies, resources such as sulfur minerals with a lower cut-offgrade, concentrates or complex metallurgical materials. The industry iseager to reach out to a technology that provides productive schemes oflow costs and that do not generate discard currents that requireexpensive neutralizing operations. The new process proposed is low cost,because the different flows in the productive circuit balance each otherand use electrowinning cells with an interface that allows ionicexchange in particular through membranes that regenerate the oxidizingagent free from copper and also produce metallic cathodes with lesselectric energy consumption in comparison to the conventional technologyapplied in the copper plants of the current industry.

Since the present invention has several potential processconfigurations, and how these can be used in multiple circuits dependingon the type of application required, it is understood that all matterherein described and illustrated in the diagrams annexed shall beconstrued by way of example. The scope of the claims should not belimited by the preferred embodiments set forth in the examples, butshould be given the broadest interpretation consistent with thedescription as a whole.

GLOSARY Units

-   t/d: Tons per day-   %: Mass percentage-   m³/d: Cubic meters per day-   g/L: Kilograms per liter-   V: Volts

Terms or Acronyms

-   EW: Electrowinning-   PLS: Pregnant Leach Solution-   SX: Solvent Extraction-   LX: Leaching Process

Example 1: Application to the Treatment of Copper and Metal Axe

Through this first example, it is shown the application of the proposedprocess to the processing of intermediate products of a foundry such asshafts, copper mattes or white metal. This particular process ispresented with reference to the flow chart in FIG. 2, which is performedat atmospheric pressure and temperature in the range of 20-90° C.

In this case, FIG. 2 shows a general scheme of the autogenous proposedprocess that leaches copper mattes and white metal axes combined to theproduction of copper cathodes. The captions of this figure correspondto:

i) Main Operations:

-   -   A-Acid-Ferric Leaching Circuit in Iron in Reactors or Piles,    -   B-Solvent Extraction Circuit and    -   C-Electrowinning circuit in cells with membranes.

ii) Currents or Main Flows: 1-White metal or copper mates or Copperaxes, 2-PLS solution, 3-Secondary Leaching Material to rework in aFoundry, 4-Raffinate Solution, 5-Rich Electrolyte, 6-Cathodes or CopperPulp, 7-Weak Electrolyte, 8-Acid-Ferrous Aqueous Solution and9-Acid-Ferric Aqueous Solution.

In this process, the compound of interest (white metal, copper mattes oraxes, corresponding to an intermediate material generated in thesmelters) is leached in the acid-ferric solution from the cell in theelectrowinning phase in cells with membrane. The rich solution generatedin the leaching step is concentrated and purified by solvent extractiontechnology, so as to generate a rich and pure electrolyte with the metalof interest, which is then reduced in an electrolyte way in order tocreate metallic cathodes.

The following table provides a summary of the material balance appliedto the treatment of white metal (FeS-Cu2S) to achieve a production ofone ton per day of copper cathode (99.999% Cu).

TABLE 1 Balance of Example 2 applied to the White Metal TreatmentVariable Unit Value Copper cathode produced (9) t/d 1 Fedwhite metal (1)t/d 1.35-1.40 Percentage of copper in white metal % 75 Solution flowraffinate/PLS (3, 4) m³/d 12-24 Solution flow acid-ferric/ferrous (2, 5)m³/d 10-15 Electrolyte flow rich/poor (7, 8) m³/d 3-4 Concentration ofdissolved iron in EW g/L 40-60 Secondary material leaching t/d≈0.04-0.08  

Example 2: Application to the Treatment of Cement, Precipitates andScrap Copper and Other Metals

Through this second example it is shown the application of the proposedprocess to the treatment of cement, precipitates and scrap metal. Thisparticular process is presented with reference to the flow chart in FIG.2, which is performed at atmospheric pressure and temperature in therange of 20-90° C.

In this case, FIG. 2 presents an overview of a General Scheme of theProposed Autogenous Process to Leach Cement or Precipitates and CopperScrap combined with the Production of Copper Cathodes. The captions ofthis figure correspond to:

i) Main Operations:

-   -   A-Acid-Ferric Leaching Circuit in Reactors or Piles,    -   B-Solvent Extraction Circuits and    -   C-C-Electrowinning Circuit in Cells with Membrane

ii) Currents or Main Flows: 1-Cement or scrap copper, 2-PLS solution,3-Residual Material Disposal, 4-Raffinate Solution, 5-Rich Electrolyte,6-Cathodes or Copper Pulp 7-Weak Electrolyte, 8-Acid-Ferrous AqueousSolution and 9-Acid-Ferric Aqueous Solution.

In this process the compound of interest (cement, precipitated or copperscrap) is leached in the acid-ferric solution from the electrowinningphase in cells with membrane. The rich solution generated in theleaching step is concentrated and purified by solvent extractiontechnology, so as to generate a rich and pure electrolyte with the metalof interest, which is then reduced in an electrolyte way in order tocreate metallic cathodes.

The following table provides a summary of the material balance appliedto the processing of copper cement in order to achieve the production of1 ton per day of copper cathode (99.999% Cu).

TABLE 2 Balances in Example 2 applied to the Treatment of Copper CementVariable Unit Value Copper cathode produced (9) t/d 1 Fed white metal(1) t/d 1.4 Percentage of copper in white metal % 75 Solution flowraffinate/PLS (3, 4) m³/d 12-24 Solution flow acid-ferric/ferrous (2, 5)m³/d 10-15 Electrolyte flow rich/poor (7, 8) m³/d 3-4 Concentration ofdissolved iron in EW g/L 40-60 Leaching discard material disposal (6)t/d ≈0.1-0.2  

Example 3: Application to the Treatment of Copper Concentrates, Tailingsand Smelter Dusts

Through this third example it is shown the application of the proposedprocess to the treatment of metal concentrates. This particular processis presented with reference to the flow chart in FIG. 2, which isperformed at atmospheric pressure and temperature in the range of 20-90°C.

In this case FIG. 2 shows a General Scheme of the Proposed AutogenousProcess for Leaching Copper Concentrates, Casting Powder and/or Tailingscombined with the Production of Copper Cathodes. The captions of thisfigure correspond to:

i) Main Operations: A-Acid-Ferric Leaching Circuit in Reactors or PilesB-Solvent Extraction Circuit and C-Electrowinning Circuit in Cells withMembranes.

ii) Currents or Main Flows: 1-Copper Concentrates, Melting Powdersand/or Tailings, 2-PLS solution, 3-Secondary Disposal Material or reworkleaching in the Smelter, 4-Raffinate Solution, 5-Rich Electrolyte,6-Cathodes or Copper Pulp, 7-Weak Electrolyte, 8-Acid-Ferrous AqueousSolution and 9-Acid-Ferric Aqueous Solution.

In this process the compound of interest (copper concentrates, tailingsand smelter dusts) is leached in the acid-ferric solution from theelectrowinning phase in cells with membrane. The rich solution generatedin the leaching step is concentrated and purified by solvent extractiontechnology, so as to generate a rich and pure electrolyte with the metalof interest, which is then reduced in an electrolyte way in order tocreate metallic cathodes.

The following table provides a summary of the material balances appliedto processing of copper concentrate (composition 10% Cu2S, CuS 10%, 45%CuFeS2, Fe2S 25%, 5% gangue) considering a partial leaching of copper50% to achieve production of 1 ton per day of copper cathode (99.999%Cu).

TABLE 3 Balance of Example 2 applied to the treatment of CopperConcentrate Variable Unit Value Copper cathode produced (9) t/d 1 Fedwhite metal (1) t/d 6.9 Percentage of copper in white metal % 30.2Solution flow raffinate/PLS (3, 4) m³/d 15-20 Solution flowacid-ferric/ferrous (2, 5) m³/d 10-15 Electrolyte flow rich/poor (7, 8)m³/d 3-4 Concentration of dissolved iron in EW g/L 40-60 Secondarymaterial to rework (6) t/d ≈5.3

Example 4: Application for the Treatment of copper Sulfide Minerals

Through this fourth example it is shown the application of the proposedprocess to treat low-grade sulfide ores. This particular process ispresented with reference to the flow chart in FIG. 2, which is performedat atmospheric pressure and temperature in the range of 20-60° C.

In this case FIG. 2 presents an overview of a General Scheme of theProposed Autogenous Process to Leach Cement or Precipitates and CopperScrap combined with the Production of Copper Cathodes. The captions ofthis figure correspond to:

i) Main Operations: A-Acid-Ferric Leaching Circuit in Reactors orBatteries or Dumps, B-Solvent Extraction Circuit and C-ElectrowinningCircuit in Cells with Membranes.

ii) Currents or Main Flows: 1-Copper Sulfide Ores 2-PLS Solution3-Leaching discharge, 4-Raffinate Solution, 5-Rich Electrolyte,6-Cathodes or Copper Pulp 7-Weak Electrolyte, 8-Acid-Ferrous AqueousSolution and 9-Acid-Ferric Aqueous Solution.

In this process the compound of interest (copper sulfide minerals) isleached in the acid acid-ferric solution from the Electrowinning phasein cells with membrane. The rich solution generated in the leaching stepis concentrated and purified by solvent extraction technology, so as togenerate a rich and pure electrolyte with the metal of interest, whichis then reduced in an electrolyte way in order to create metalliccathodes.

The following table provides a summary of the material balances appliedto processing of copper ore of low grade (0.4% composition Cu2S, CuS0.3%, 0.3% CuFeS2, Fe2S 3%, 96% gangue) considering a leaching 50% ofcopper so as to achieve a production of one ton per day of coppercathode (99.999% Cu).

TABLE 4 Balance of Example 2 applied to the Copper Ore ProcessingVariable Unit Value Copper cathode produced (9) t/d 1 Fed white metal(1) t/d 323 Percentage of copper in white metal % 0.62 Solution flowraffinate/PLS (3, 4) m³/d 480 Solution flow acid-ferric/ferrous (2, 5)m³/d 30-45 Electrolyte flow rich/poor (7, 8) m³/d 100-150 Concentrationof dissolved iron in EW g/L 40-60 Secondary material or gravel todisposal (6) t/d ≈320

Example 5: Application to Treatment Material Processing, Minerals andCompounds Formed with Other Metals, such as Zinc, Iron, Cobalt,Molybdenum and Nickel

Through this fifth example it is shown the application of the processproposed to the treatment of mineral or metallic materials containingcopper, zinc, iron, cobalt, molybdenum and/or nickel. This particularprocess is presented with reference to the flow chart in FIG. 2, whichis performed at atmospheric pressure and temperature in the range of20-90° C.

In this case FIG. 2 shows a General Scheme of the Proposed AutogenousProcess to Leach Materials, Minerals and compounds formed by zinc, iron,cobalt, molybdenum, copper and/or nickel production combined with themetallic cathode.

i) Main Operations: A-Acid-Ferric Leaching Circuit in Reactors or Pilesor Dumps, B-Solvent Extraction Circuit, C-Electrowinning Circuit InCells with Membrane.

ii) Currents or Main Flows: 1-Metals and Minerals Sulfur(Cu/Fe/Zn/Co/Ni), 2-PLS Solution, 3-Secondary Leaching Material todiscard (Floating/Leach/Cast), 4-Raffinate Solution, 5-Rich Electrolyte,6-Cathodes or Metal Pulp (Cu/Zn/Fe/Co/Mo/Ni), 7-Weak Electrolyte,8-Acid-Ferrous Aqueous Solution 9-Acid-Ferric Aqueous Solution.

In this process the compound of interest (ores, concentrates andmaterials of zinc, cobalt and/or nickel) is leached in the acid-ferricsolution from the electrowinning phase in cells with membrane. The richsolution generated in the leaching step is concentrated and purified bysolvent extraction technology, so as to generate a rich and pureelectrolyte with the metal of interest, which is then reduced in aelectrolyte way in order to create electrolytic metal cathodes.

The material balance for this case will depend on the type ofmetallurgic metal or mineral to be processed, so as to adjust thesolvent extraction and electrowinning operations to the productionrequirement, thereby generating the amount of oxidant (ferric sulfate)in the right measure for the leaching requirement.

In the case of treating materials of molybdenum (concentrates and/orminerals), this process allows dissolving the impurities associated withcopper, zinc, iron, among others, in order to leave a clean solidproduct (concentrate and/or molybdenum ore) for further processing byroasting and/or leaching technology in order to recover the molybdenumcontent.

BIBLIOGRAPHY

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1. A metallurgical method for operating an autogenous production circuitfor producing metal(s), said method using one or more oxidizing agentsgenerated electrolytically in a cell with one or more interfaces whichallows anion exchange; said method comprising steps of: (a) leaching ofmineral(s) or material(s) containing at least one metal of interest (LX)in a first cell (A) to produce a pregnant leach solution (2) and anacid-ferrous aqueous solution (8); (b) using solvent extractionprocess(es) or selection process(es) in a second cell (B) to concentratesaid metal(s) of interest (SX) of said pregnant leach solution (2) toproduce a rich electrolyte (5) and a raffinate solution (4), saidraffinate solution (4) being recycled in said first cell (A); and (c)electrowinning (EW) in a third cell (C) of said rich electrolyte (5)received from said second cell (B) and said acid-ferrous aqueoussolution (8) received from said first cell (A), for producing a metalcathode (6) and an acid-ferric acid solution (9), said acid-ferric acidsolution (9) being recycled in said first cell (A), wherein said steps(a), (b) and (c) are performed in said autogenous circuit that includessaid first, second and third cells (A, B, C) with one or more anionicinterfaces producing anodic and cathode reactions.
 2. The method ofclaim 1, wherein during said step (c) of electrowinning, said richelectrolyte (5) and said acid-ferrous aqueous solution (8) that has thelowest ion valence of the oxidizing agent(s) enter into the third cell(C) and wherein use of a power field allows the reduction of the metaldissolved in the cathode and the simultaneous oxidation of the agent(s)that turn into dissolved oxidizing agent(s) over the surface of an anodeand this oxidizing agent is recycled into the circuit so it can bereused in said step of (a) leaching.
 3. The method of claim 2, whereinthe power field includes at least one of electric current, magneticfield and combinations thereof.
 4. The method according to claim 1,wherein said one or more oxidizing agent includes ferric sulfate,wherein said at least one metal of interest includes copper, wherein anelectrolytic cell membrane semi-reactions of said interfaces are givenby : i) anodic reaction: 2Fe²⁺--->2e+2Fe³⁺ ii) cathode reaction:Cu2++2e--->Cu°, and wherein a selective ionic exchange of sulfate ion(S₂ ⁻⁴) occurs.
 5. The method according to claim 1, further comprisingsteps of: extracting or incorporating mass flow (M) in said acid-ferricacid solution (9) from said third cell (C) before being recycled in saidfirst cell (A); and extracting or incorporating energy (E) from saidacid-ferrous aqueous solution (8) received from said first cell (A)before being sent to said third cell (C).
 6. The method according toclaim 5, wherein said mass flow (M) includes iron or sulfur metals andsaid energy includes heating energy or other type of energy.
 7. Themethod according to any one of claims 1 to 6, comprising using twocircuits of leaching solutions combining said step (a) of leaching, andsaid step (b) of using solvent extraction or concentration of themetal(s) or material(s) of interest and said step (c) ofelectrowinninging said cells with interfaces, so as to purify said richelectrolyte (5) of the metal(s) or material(s) of interest to obtainhigh quality metal cathodes and at the same time to regenerate in abalanced way a leaching solution through oxidizing agent(s) used todissolve or leach material(s) or mineral(s) in the production process.8. The method according to any one of claims 1 to 7, comprising using ofa selective anionic interface or interfaces for exchanging the ions ofinterest.
 9. The method according to any one of claims 1 to 8,comprising using anolyte and catholyte chambers in the electrowinningcell (C).
 10. The method according to any one of claims 1 to 9 for usein an autogenous productive circuit configuration for the production ofsulfur metals and materials that use ferric sulfate as an oxidizingagent generated electrolytically in a cell with ionic exchange membrane,said method comprising steps of: (a) acid-ferric leaching of the mineralor material including at least one of compounds, concentrates, tailings,white metal, cements, precipitates, scrap and sulfur minerals, through aconventional system of piles/dumps/reactors/vats; (b) solvent extraction(SX) to separate a rich electrolyte coming from the metal of interest(Cu, Mn, Zn, Co, Mo, Ni, etc.), (c) electrowinning (EW) done in acircuit of cells with anionic membranes for the production of MetalCathodes.
 11. The method according to claim 10, comprising using of twoleaching solution circuits combining operations of leaching, solventextraction and electrowinning in cells with membranes, to purify anelectrolyte rich in copper in order to obtain metal cathodes of highquality and at the time regenerate in a balanced way the Leachingsolution of ferric sulfate in a sulfuric environment which is used todissolve or leach the materials or minerals within the productiveprocess.
 12. The method according to claim 10, comprising applying saidsteps to the processing of matte, shaft or white metal in piles oragitated reactors, which operates in a 20-90° C. range, using solutionswith 10-200 g/L of sulfuric acid and 10-100 g/L of dissolved ironregenerated through electrowinning in membrane cells.
 13. The methodaccording to claim 10 for use in processing of copper concentrates andsmelter dust agitated reactors, which operate in a 20-90° C. range,using solutions with 10-200 g/L of sulfuric acid and 10-100 g/L ofdissolved iron regenerated through electrowinning in membrane cells. 14.The method according to claim 10 for use in processing of copper cementand copper scrap in piles and agitated reactors, which operate in a20-90° C. range, using solutions with 10-200 g/L of sulfuric acid and10-100 g/L of dissolved iron regenerated through electrowinning inmembrane cells.
 15. The method according to claim 10 for use inprocessing of sulfur minerals in piles and dumps, which operate in a20-90° C. range, using solutions with 10-200 g/L of sulfuric acid and10-100 g/L of dissolved iron regenerated through electrowinning inmembrane cells.
 16. The method according to claim 10 for use inprocessing of materials, minerals and compounds formed by otherminerals, such as Zn, Fe, Co, Mn, Mo and Ni in piles and agitatedreactors, which operate in a 20-90° C. range, using solutions with10-200 g/L of sulfuric acid and 10-100 g/L of dissolved iron regeneratedthrough electrowinning in membrane cells.
 17. The method according toclaim 10 for use in two leaching solution circuits combining the stepsof leaching, solvent extraction and electrowinning in membrane cells, topurify an electrolyte rich in silver or gold in order to obtain metalcathodes of high quality and at the time regenerate in a balanced waythe Leaching solution of ferric sulfate or zinc sulfate in an sulfuricenvironment which are used to dissolve or leach the materials orminerals within the productive process.
 18. The method according toclaim 10 for use in a separation and gathering process for gold and/orsilver, which operates in a 5-100° C. range, using solutions with 10-500g/L of acids and/or bases and that it is at the same time regeneratedduring the process through electrowinning and producing cathodes withprecipitate of the metal of interest in cells with membranes thatselectively allow the pass of anions and cations.